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Assembly of air-stable copper(I) alkynide nanoclusters assisted by tripodal polydentate phosphoramide ligands

Nature Synthesis volume 3, pages 517–526 (2024)Cite this article

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Abstract

Copper(I) nanoclusters are attractive due to their potential applications, but their synthesis remains challenging due to susceptibility to oxidation and the lack of mature synthetic methods. Here, by introducing a bifunctional phosphoramide ligand, N,N′,N′-tris(2-pyridinyl)phosphoric triamide [PO(NHPy)3], into the Cu/RC≡CH assembly system, we construct two high-nuclearity Cu(I) nanoclusters (Cu62 and Cu12). Single-crystal X-ray structural analysis reveals that multidentate phosphoramide ligands enhance the stability of Cu(I) nanoclusters through cooperation of hydrogen and coordination bonding. Cu62 is a four-layered (C2)@Cu8@(C2)12@Cu54 core, where acetylenediide (C22−) ions from alkynol ligands are inserted betwen two Cu shells (inner Cu8 and outer Cu54 shells). By changing alkynol to another cycloalkyl alkyne lacking the OH group, Cu12 without C22− ion was isolated, demonstrating the promotion of C22− release by hydroxyl group in the above assembly system. We show the universality of the synthetic method by isolating two additional nanoclusters (Cu32 and Cu24). Cu62 exhibits good degradation performance for various dyes due to the generation of reactive oxygen species (·OH). This work presents a generalized strategy for constructing high-nuclearity Cu(I) alkynyl nanoclusters at room temperature.

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Fig. 1: Synthetic routes for Cu62, Cu32, Cu24 and Cu12.
Fig. 2: Structural anatomy of Cu62.
Fig. 3: The detailed analysis of C22− ions in Cu62.
Fig. 4: The detailed analysis of ligands in Cu62.
Fig. 5: The detailed structure analysis for Cu12 nanocluster.
Fig. 6: Optical behaviour and the underlying mechanisms.
Fig. 7: Photocatalysis behaviour and the underlying mechanisms.

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Data availability

All data supporting the findings of this study are included within the article and its Supplementary Information. Source data are provided with this paper. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2237942 (Cu62), 2237943 (Cu12), 2290356 (Cu32) and 2290357 (Cu24). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant nos. 22325105, 22171164 and 52261135637 to D.S.; 22201159 to Z.W.), the Natural Science Foundation of Shandong Province (nos. ZR2019ZD45, ZR2020ZD35, JQ201803 and ZR2017MB061), the Taishan Scholar Project of Shandong Province of China (nos. tsqn201812003 and ts20190908), the National Postdoctoral Innovative Talents Support Program (no. BX2021171) and China Postdoctoral Science Foundation (no. 2021M700081).

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, State Key Laboratory of Crystal Materials, Shandong University, Jinan, People’s Republic of China

    Hui Zhao, Chengkai Zhang, Baoliang Han, Zhi Wang, Yicheng Liu, Chen-Ho Tung & Di Sun

  2. Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, and School of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng, People’s Republic of China

    Qingwang Xue

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Contributions

The original idea was conceived by D.S.; experiments and data analyses were performed by H.Z. and D.S.; DFT calculations and relevant data analyses were performed by C.Z., B.H. and H.Z.; structure characterization was performed by H.Z., Z.W. and D.S.; and the paper was drafted by D.S., H.Z., C.Z., B.H., Z.W., Y.L., Q.X. and C.-H.T. All authors have given approval to the paper.

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Correspondence to Di Sun.

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The authors declare no competing interests.

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Nature Synthesis thanks the anonymous reviewers for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–41 and Tables 1–9.

Supplementary Data 1

Crystallographic data of Cu62, CCDC 2237942.

Supplementary Data 2

Crystallographic data of Cu32, CCDC 2290356.

Supplementary Data 3

Crystallographic data of Cu12, CCDC 2237943.

Supplementary Data 4

Crystallographic data of Cu24, CCDC 2290357.

Source data

Source Data Fig. 6

Data of solid-state UV–vis, varied-temperature luminescence, and PDOS.

Source Data Fig. 7

Data of photocurrent responses, EIS, photocatalysis and ESR.

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Zhao, H., Zhang, C., Han, B. et al. Assembly of air-stable copper(I) alkynide nanoclusters assisted by tripodal polydentate phosphoramide ligands. Nat. Synth 3, 517–526 (2024). https://doi.org/10.1038/s44160-023-00467-4

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